CN104003711B - Dielectric ceramic composition and electronic unit - Google Patents

Dielectric ceramic composition and electronic unit Download PDF

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Publication number
CN104003711B
CN104003711B CN201410064852.7A CN201410064852A CN104003711B CN 104003711 B CN104003711 B CN 104003711B CN 201410064852 A CN201410064852 A CN 201410064852A CN 104003711 B CN104003711 B CN 104003711B
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oxide compound
ceramic composition
converted
dielectric
dielectric ceramic
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CN104003711A (en
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森崎信人
佐佐木孝
福冈智久
松永裕太
小松和博
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TDK Corp
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TDK Corp
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Abstract

Even if the invention provides a kind of strength of electric field put on dielectric layer in raising, and also can show dielectric ceramic composition and the electronic unit of good characteristic when increasing the stacked number of laminated ceramic capacitor.This dielectric ceramic composition, containing perovskite-type compounds (ABO 3), contain following material relative to 100mol compound: during to be converted into each oxide compound, contain Ra 2o 3(Ra is more than at least a kind of being selected from Dy, Gd and Tb) 0.6 ~ 1.4mol; Rb 2o 3(Rb is Ho and/or Y) 0.2 ~ 0.7mol; Rc 2o 3(Rc is at least a kind of being selected from Yb and/or Lu) 0.2 ~ 0.7mol; It is the oxide compound of the Mg of 0.6 ~ below 1.6mol when being converted into Mg; And be that 0.6 ~ 1.2mol(does not comprise 1.2 when being converted into Si) the compound of Si.

Description

Dielectric ceramic composition and electronic unit
Technical field
The present invention relates to dielectric ceramic composition and there is the ceramic electronic components of the dielectric layer be made up of this dielectric ceramic composition.
Background technology
As an example of ceramic electronic components laminated ceramic capacitor by as small-sized and high-performance and the electronic unit with high reliability be widely used.Utilized in a large number on electric installation and electronics especially.In the last few years, with electric installation and electronics miniaturization and high performance, to the requirement of the raising of the further miniaturization of laminated ceramic capacitor, high performance and reliability in raising.Propose there is the laminated ceramic capacitor recorded in patent documentation 1,2 as the laminated ceramic capacitor reaching such requirement.
But in the last few years, the miniaturization more of laminated ceramic capacitor, the requirement of bulky capacitor, in raising, needed the thin layer of dielectric layer, multiple stratification.
Therefore, even if to also obtaining the demand of the dielectric ceramic composition of sufficient reliability and good temperature profile in increase when thin layer, multiple stratification.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 10-223471
Patent documentation 2: Japanese Patent Laid-Open 2011-201761
Summary of the invention
The technical problem that invention will solve
The present invention is based on such practical situation to complete, even if provide when by dielectric layer than the more thin layer strength of electric field making to put on dielectric layer improves in the past, or when adding the dielectric medium number of plies, also meet dielectric ceramic composition and the electronic unit of good temperature profile and sufficient reliability.
In order to achieve the above object, dielectric ceramic composition involved in the present invention is characterised in that, as main component, contains with general formula ABO 3the compound of the perovskite type crystal structure represented by (A is at least a kind of being selected from Ba, Ca and Sr, and B is at least a kind of being selected from Ti and Zr), contains relative to 100mol above-claimed cpd as minor component, is converted into Ra 2o 3be the oxide compound (Ra is at least a kind of being selected from Dy, Gd and Tb) of the Ra of 0.6 ~ 1.4mol, be converted into Rb 2o 3be the oxide compound (Rb is at least a kind of being selected from Ho and Y) of the Rb of 0.2 ~ 0.7mol, be converted into Rc 2o 3be the oxide compound (Rc is at least a kind of being selected from Yb and Lu) of the Rc of 0.2 ~ 0.7mol, to be converted into oxide compound that magnesium is the Mg of 0.6 ~ 1.2mol, to be converted into Si be that 0.6 ~ 1.2mol(does not comprise 1.2mol) the oxide compound of Si.
In addition, the total amount of above-mentioned Ra, Rb, Rc is converted into Ra respectively 2o 3, Rb 2o 3, Rc 2o 3for more than 1.5mol below 2.4mol, and the molar ratio of the oxide compound of the oxide compound of Ra, Mg, the oxide compound of Si is preferably positioned at an A(28,34,38), some B(37,27,37), some C(41,35,24), some D(27,46,27) these four somes scope of surrounding.
As minor component, the preferred oxide compound of at least a kind be selected from V, Mo and W containing when being converted into V, Mo and W being 0.05 ~ 0.10mol further.
As minor component, the preferred oxide compound containing when being converted into Mn and Cr being Mn and/or Cr of 0.10 ~ 0.20mol further.
In addition, the preferred median size of dielectric ceramic composition of the present invention is 150nm ~ 260nm.In addition, preferred Ba/Ti=1.004 ~ 1.015.
In addition, ceramic electronic components involved in the present invention has the dielectric layer and electrode layer that are made up of above-mentioned dielectric ceramic composition.
Accompanying drawing explanation
Fig. 1 is the sectional view of the laminated ceramic capacitor involved by an embodiment of the invention.
Fig. 2 is in the sample 1 ~ 40 of illustrated embodiment 1, the triangular plot of the scope sample within the scope of the invention of the oxide compound of the oxide compound of Ra, the oxide compound of Rb, Rc, the oxide compound of Mg, the oxide compound of Si.
Nomenclature
1: laminated ceramic capacitor
2: dielectric layer
3: interior electrode layer
4: outer electrode
10: capacitor element main body
Embodiment
As shown in Figure 1, there is as the laminated ceramic capacitor 1 of an example of monolithic ceramic electronic component the capacitor element main body 10 of dielectric layer 2, the alternately laminated formation of interior electrode layer 3.The mode that interior electrode layer 3 alternately exposes on the surface of the 2 relative ends of capacitor element main body 10 with each end face is stacked.Pair of external electrodes 4 is formed on the both ends of capacitor element main body 10, and be connected to the interior electrode layer 3 of alternately configured expose end face, form capacitor loop.
The shape of capacitor element main body 10 is not particularly limited, and usually makes rectangular parallelepiped as shown in Figure 1.In addition, its size without particular limitation of.
The dielectric ceramic composition of dielectric layer 2 involved by present embodiment is formed.In dielectric ceramic composition involved in the present embodiment, as main component, there is general formula ABO 3compound represented by (A is at least a kind of being selected from Ba, Ca and Sr, and B is at least a kind of being selected from Ti and Zr).In addition, dielectric ceramic composition has main component is ABO 3dielectric particle.
As general formula ABO 3the object lesson of represented compound, can enumerate { (Ba 1-x-yca xsr y) O} u(Ti 1-zzr z) vo 2represented compound.In addition, u, v, x, y, z all can in arbitrary scopes, preferably in following scope.
In above-mentioned formula, x is preferably 0≤x≤0.1, more preferably 0≤x≤0.05.By making x in above-mentioned scope, the temperature profile of the dielectric layer be made up of dielectric ceramic composition involved in the present invention or relative permittivity can be controlled in preferable range.If x is excessive, then the relative permittivity of medium layer has and becomes too low tendency.In addition, in the present embodiment, not necessarily containing Ca.That is, x can be 0.
In above-mentioned formula, y is preferably 0≤y≤0.1, more preferably 0≤y≤0.05.By making y in above-mentioned scope, the relative permittivity of the dielectric layer be made up of dielectric ceramic composition involved in the present invention can be improved.If y is excessive, then the temperature profile of dielectric layer has the tendency of variation.In addition, in the present embodiment, not necessarily containing Sr.That is, y can be 0.
In above-mentioned formula, z is preferably 0≤z≤0.3, more preferably 0≤z≤0.15.By z in above-mentioned scope, the relative permittivity of the dielectric layer be made up of dielectric ceramic composition involved in the present invention can be improved.If z is excessive, then the temperature profile of dielectric layer has the tendency of variation.In addition, in the present embodiment, not necessarily containing Zr.That is, z can be 0.
In addition, ratio Ba/Ti=1.004 ~ 1.015 of Ba and Ti contained in preferred dielectric ceramic composition, more preferably 1.007 ~ 1.012.If Ba/Ti is too high, then have sintering abundant not, relative permittivity can reduce, the tendency that reliability also reduces, if Ba/Ti is too low, then has and burns till stability and can be deteriorated, the tendency that temperature profile is deteriorated.
Dielectric ceramic composition involved in present embodiment, outside above-mentioned main component, contains the oxide compound of the oxide compound of the oxide compound of Ra and the oxide compound of Rb and Rc, the oxide compound of Mg and Si as minor component.At this, Ra is at least a kind of being selected from Dy, Gd and Tb.Rb is at least a kind of being selected from Ho and Y.Rc is at least a kind of being selected from Yb and Lu.
If by the ABO of the oxide compound of Ra relative to 100mol 3content as α, then α is converted into Ra 2o 3for more than 0.6mol below 1.4mol, be preferably more than 0.7mol below 1.2mol.If α is too much, then has relative permittivity and reduce, the tendency that temperature profile is deteriorated.If contrary very few, then there is the tendency of variation in the high temperature load life-span of dielectric layer.In addition, particularly preferably Dy is contained as Ra.
If by the ABO of the oxide compound of Rb relative to 100mol 3content as β, then β is converted into Rb 2o 3for more than 0.2mol below 0.7mol, be preferably more than 0.2mol below 0.6mol.If β is too much, then the relative permittivity having dielectric layer reduces, the tendency that the high temperature load life-span is deteriorated.If contrary very few, the temperature profile of dielectric layer has the tendency of variation.In addition, particularly preferably Ho is contained as Rb.
If by the ABO of the oxide compound of Rc relative to 100mol 3content as γ, then γ is converted into Rc 2o 3for more than 0.2mol below 0.7mol, be preferably more than 0.2mol below 0.5mol.If γ is too much, then the relative permittivity having dielectric layer reduces, the tendency that the high temperature load life-span is deteriorated.If contrary very few, the temperature profile of dielectric layer has the tendency of variation.In addition, particularly preferably Yb is contained as Rc.
In addition, the total amount RT of α, β, γ is converted into Ra respectively 2o 3, Rb 2o 3, Rc 2o 3be preferably more than 1.5mol below 2.4mol, more preferably more than 1.5mol and below 2.0mol.If RT is too much, then Ra, Rb, Rc segregation in the dielectric layer, therefore there is the tendency of variation in the high temperature load life-span.On the contrary, if very few, the temperature profile of dielectric layer has the tendency of variation.
In the present embodiment, at ABO 3for in the dielectric particle of main component, solid solution has the metallic element of minor component, such as Ra, Rb, Rc.In addition, dielectric particle preferably has so-called nucleocapsid structure, also can contain the particle of complete solid solution class.
In the present embodiment, specific rare earth element is categorized as Ra, Rb, Rc, the value of the effective ionic radius during hexa-coordinate of this classification based on rare earth element is carried out.For effective ionic radius, and the little rare earth element of the difference of A site atom easily replaces (being solid-solution in) A site, and the large rare earth element of the difference of A site atom has the tendency being difficult to replace (being solid-solution in) A site.
In the present embodiment, and the little rare earth element of the difference of the ionic radius of A site atom is equivalent to Ra, and the large rare earth element of difference is equivalent to Rc, in Ra and Rc, is solid-solution in ABO 3degree different, Ra has and is solid-solution in ABO completely 3in tendency.Rc has and is only solid-solution in ABO 3surrounding position, namely easily form the tendency of so-called nucleocapsid structure.If although Ra makes an addition in dielectric ceramic composition by its result, can improve the high temperature load life-span of dielectric ceramic composition, temperature profile has the tendency of variation.On the other hand, if made an addition in dielectric composition by Rc, although the temperature profile of dielectric ceramic composition then can be made to become good, there is the tendency of variation in the high temperature load life-span.In addition, the difference of the ionic radius of Rb and A site atom is roughly in the centre of Ra and Rc.
In the present embodiment, by regulating the content of Ra, Rb, Rc tri-kinds of rare earth element groups can the solid solution condition of control Ra, Rb, Rc, good temperature profile and excellent high temperature load life-span be taken into account.
In addition, in the present embodiment, in dielectric ceramic composition, the oxide compound further containing Mg.The oxide content of Mg is relative to the ABO of 100mol 3, being converted into MgO is 0.6 ~ 1.2mol, more preferably 0.7 ~ 1.1mol.If the content of the oxide compound of Mg is too much, then there is the tendency of variation in the high temperature load life-span of dielectric layer.If contrary very few, then the abnormal grain of dielectric particle can be caused to grow up, and the temperature profile of dielectric layer has the tendency of variation.
In addition, in the present embodiment, the oxide compound further containing Si in dielectric ceramic composition.The oxide compound of Si, mainly plays the effect as sintering aid.The content of the oxide compound of Si is equivalent to the ABO of 100mol in addition 3, be converted into Si and be more than 0.6mol and be less than 1.2mol, more preferably more than 0.8mol and below 1.1mol.If the oxide compound of Si is too much, then the temperature profile of high temperature load life-span and dielectric layer has the tendency of variation.In addition, if the oxide compound of Si is very few, then high temperature load life-span and CR amass the tendency of variation.In addition, in the application's embodiment, containing composite oxides in oxide compound.
Based on more than, in the present embodiment, by by the overall control of rare earth element Ra, Rb and Rc at the ABO relative to 100mol 3for more than 1.5mol and below 2.4mol, thus relative permittivity improves and the design of the layer thickness of dielectric layer can be thickeied, and therefore improve the life-span of ceramic electronic components further.In addition, by the ratio of the oxide compound of the oxide compound of the oxide compound of control Ra, Rb, the oxide compound of Rc, the oxide compound of Mg and Si, desired temperature characteristics of capacitance can be maintained, and improve the life-span further.
Dielectric ceramic composition described in present embodiment, as minor component preferably further containing the oxide compound of more than at least a kind that is selected from V, Mo and W, the oxide compound of Mn and/or Cr.By containing above-mentioned composition, characteristic can be improved further.In the present embodiment, Mn is more preferably from the viewpoint of reliability compared to Cr.
Be selected from the content of the oxide compound of at least a kind in V, Mo and W, relative to the ABO of 100mol 3, convert with V, Mo and W, be preferably more than 0.03mol and below 0.10mol, more preferably more than 0.05mol and below 0.09mol, if the content of above-mentioned oxide compound is too much, then insulation resistance (CR amasss) has the tendency of reduction.In addition, preferably V is used in the present embodiment.
In addition, the content of the oxide compound of Mn and/or Cr, relative to the ABO of 100mol 3, be converted into Mn and/or Cr and be preferably more than 0.10mol and below 0.20mol.No matter too much or very few the content of the oxide compound of Mn and/or Cr is, and insulation resistance (CR amasss) has the tendency of reduction.
Dielectric particle contained in dielectric ceramic composition described in present embodiment average crystallite particle diameter after the sintering without particular limitation of, in order to the thin layer requirement according to dielectric layer, be preferably 150 ~ 260nm, more preferably 170 ~ 250nm.If average crystallite particle diameter is little, then has relative permittivity and reduce, the tendency that temperature profile is deteriorated.In addition, if average crystallite particle diameter is large, then the high temperature load life-span has the tendency of variation.In addition, the dielectric ceramic composition involved by present embodiment, according to desired characteristic, can contain other composition further.
The thickness of the dielectric layer involved by present embodiment without particular limitation of, be preferably more than 1.0 μm and less than 10.0 μm.
The stacked number of dielectric layer without particular limitation of, be preferably more than 20, more preferably more than 50, be particularly preferably more than 100.The upper limit of stacked number without particular limitation of, be such as preferably about 2000.
Electro-conductive material contained by interior electrode layer without particular limitation of, owing to forming the material of dielectric layer, there is reducing resistance, less expensive base metal can be used.As the base metal that electro-conductive material uses, preferred Ni or Ni alloy.As Ni alloy, be preferably selected from the element of more than a kind in Mn, Cr, Co and Al and the alloy of Ni, in alloy, Ni content is preferably more than 95 % by weight.In addition, in Ni or Ni alloy, each trace ingredients containing P etc. can add up to less than about 0.1 % by weight.The thickness of interior electrode layer can appropriate change according to purposes, without particular limitation of.Be generally 0.1 ~ 3.0 μm, be preferably 0.5 ~ 2.0 μm.
Electro-conductive material contained in outer electrode without particular limitation of, cheap Ni, Cu or their alloy can be used in the present embodiment.The thickness of outer electrode 4 suitably can determine according to purposes etc., is usually preferably about 10 ~ 50 μm.
(manufacture method of laminated ceramic capacitor 1)
The laminated ceramic capacitor 1 of present embodiment and existing laminated ceramic capacitor make raw cook by the common print process or method of tableting (sheetmethod) that use paste equally, after being burnt till, outer electrode printing or transfer printing are burnt till and manufactures.Below, manufacture method is illustrated.
First, prepare dielectric raw material (dielectric ceramic composition powder), by its coating, modulate the paste (dielectric layer paste) for the formation of dielectric layer.
As dielectric raw material, first prepare ABO 3raw material and the raw material of oxide compound of Ra, Rb and Rc.As these raw materials, oxide compound or its mixture, the composite oxides of mentioned component can be used, in addition, can suitably select by burning till the various compounds becoming above-mentioned oxide compound or composite oxides, such as carbonate, oxalate, nitrate, oxyhydroxide, organometallic compound etc., can be used in combination.As ABO 3preferred use BaTiO 3represented barium titanate.
In addition, as above-mentioned ABO 3raw material use Ba uti vo 3when represented barium titanate, u/v is preferably in the scope of 1.000≤u/v≤1.005.
ABO 3raw material except so-called solid phase method, the material etc. that various liquid phase method (such as, oxalate method, hydrothermal synthesis method, alkoxide process, sol-gel method) etc. manufactures can also be used, the material manufactured by various method.
The content of each compound in dielectric raw material, can determine in the mode of the composition being formed above-mentioned dielectric ceramic composition after burning till.In state before coating, it is about 0.1 ~ 1 μm that the particle diameter of dielectric raw material is generally median size.
Dielectric layer paste can be the coating by dielectric raw material and the mixing organic of organic vehicles, also can be by dielectric raw material and the mixing water class coating of water class medium.
Organic vehicles is the medium be dissolved in by binding agent in organic solvent.Binding agent without particular limitation of, can from ethyl cellulose, polyvinyl butyral acetal etc. for suitably selecting in the various binding agents common organic vehicles.Use organic solvent without particular limitation of, can according to print process or method of tableting etc. utilize method suitably select from the various organic solvents of Terpineol 350, diethylene glycol monobutyl ether, acetone, toluene etc.
Water class medium is medium water-soluble binder or dispersion agent etc. are dissolved in the water.The water-soluble binder used in water system medium without particular limitation of, suitably select in the various binding agents that can use from the common water class media such as polyvinyl alcohol, Mierocrystalline cellulose, water soluble acrylic resin.
Interior electrode layer paste is by by the electro-conductive material be made up of above-mentioned various conductive metal or alloy or the various oxide compounds, organometallic compound, resinate etc. that form above-mentioned electro-conductive material after burning till, and the mixing modulation of above-mentioned organic vehicles.In addition, can general purpose material be contained in interior electrode layer paste, as general purpose material without particular limitation of, preferably there is the composition same with main component.
Outer electrode paste can be modulated equally with above-mentioned interior electrode layer paste.
In above-mentioned each paste organic vehicles content without particular limitation of, usual content such as binding agent is 1 ~ 10 about % by weight, and solvent is 10 ~ 50 about % by weight.In addition, can as required containing the additive be selected from various dispersion agent, softening agent, dielectric medium, isolator etc. in each binding agent.These total contents are preferably less than 10 % by weight.
When using print process, dielectric layer paste and interior electrode layer paste are printed on the substrate of PET etc., stacked, after cutting into regulation shape, peel off from substrate and make raw cook.
In addition, when using method of tableting, using dielectric layer paste to form raw cook, printing internal electrode paste thereon and after forming internal electrode pattern, their laminations being made raw cook.
(de-binding agent condition)
De-binding agent condition without particular limitation of, preferred heat-up rate is 5 ~ 300 DEG C/h, and preferably keep temperature to be 180 ~ 400 DEG C, temperature hold-time is preferably 0.5 ~ 48 hour.In addition, the atmosphere of de-binding agent is preferably in atmosphere or in reducing atmosphere.
(firing condition)
After de-binding agent, carry out burning till of raw cook.Firing condition without particular limitation of, preferred heat-up rate is 100 ~ 1000 DEG C/h.Maintenance temperature when burning till is preferably less than 1300 DEG C, and more preferably 1150 ~ 1280 DEG C, hold-time when burning till is preferably 0.5 ~ 20 hour, more preferably 1.0 ~ 15 hours.Hold-time is too low, and densification easily becomes insufficient, if too high, the exception easily produced due to interior electrode layer sinter the fracture of the electrode caused or the variation of temperature profile caused due to the diffusion of interior electrode layer constituent material, the reduction of generation dielectric ceramic composition.
The atmosphere of burning till preferably makes reducing atmosphere.Atmosphere gas without particular limitation of, such as can by N 2and H 2mixed gas humidification use.
In addition, oxygen partial pressure when burning till suitably can determine according to the kind of the electro-conductive material in internal electrode paste, and when using the base metal of Ni or Ni alloy etc. as electro-conductive material, the oxygen partial pressure in preferred firing atmosphere is 10 -14~ 10 -10mPa.If oxygen partial pressure is too low, then can causes the abnormal sintering of the electro-conductive material of interior electrode layer, can fracture be caused.In addition, if oxygen partial pressure is too high, then internal electrode has the tendency of oxidation.Cooling rate without particular limitation of, be preferably 50 ~ 1000 DEG C/h.
(annealing conditions)
After burning till in reducing atmosphere, preferably anneal is carried out to capacitor element main body.Annealing is the process in order to be carried out reoxidizing by dielectric layer, can significantly improve the insulation resistance (IR) of dielectric layer like this, also can improve reliability (IR life-span).
Annealing atmosphere without particular limitation of, preferably oxygen partial pressure is decided to be 10 -9~ 10 -5mPa.If oxygen partial pressure is too low, dielectric layer is difficult to reoxidize, if too high, internal electrode has the tendency of oxidation.
Anneal time maintenance temperature without particular limitation of, be preferably less than 1100 DEG C, be particularly preferably 950 ~ 1090 DEG C.If keep temperature too low, the oxidation of dielectric layer easily becomes insufficient, and the insulation resistance (IR) of dielectric layer reduces the tendency that reliability (IR life-span) also has reduction.If keep on the other hand temperature too high, then not only interior electrode layer oxidation and the electric capacity of electrical condenser easily reduces, and interior electrode layer and dielectric layer reaction, easily produce the variation of the temperature profile of dielectric layer, the reduction of IR, the reduction in IR life-span.In addition, annealing operation can be only made up of temperature-rise period and temperature-fall period.That is, soaking time can be set to zero.In this case, keep temperature identical with top temperature.
As annealing conditions other than the above, temperature hold-time is preferably 0 ~ 20 hour, and more preferably 2 ~ 4 hours, cooling rate was preferably 50 ~ 1000 DEG C/h, more preferably 100 ~ 600 DEG C/h.The atmosphere gas of annealing in addition without particular limitation of, such as can use the N of humidification 2gas.
In above-mentioned de-adhesive treatment, burn till and anneal, in order to by N 2the humidification such as gas or mixed gas, such as, can use humidifier etc.When using humidifier, preferred water temperature is about 5 ~ 75 DEG C.
Take off adhesive treatment, burn till, anneal and can carry out continuously, also can separately carry out.
(embodiment 1)
First, as ABO 3material powder prepare median size be the BaTiO of 200nm 3powder (u/v=1.004), the oxide raw material as Ra prepares Dy 2o 3powder, the raw material as the oxide compound of Rb prepares Ho 2o 3powder, the raw material as the oxide compound of Rc prepares Yb 2o 3powder.In addition, the raw material as the oxide compound of Ba prepares BaCO 3powder, the raw material as the oxide compound of Mg prepares MgO powder, and the raw material as the oxide compound of Mn prepares MnCO 3powder, the raw material as the oxide compound of V prepares V 2o 5powder, prepares SiO as sintering aid 2powder.
Next, weigh each raw material powder of above-mentioned preparation according to the amount shown in table 1, pulverize by the wet mixing that ball mill carries out 20 hours, dry, obtain dielectric raw material.In addition, BaCO 3and MnCO 3be contained in dielectric ceramic composition with BaO, MnO respectively after burning till.Add 0.6mol%BaCO 3to make the Ba/Ti ratio after sintering for 1.010.
Next, dielectric raw material using obtaining: 100 mass parts, polyvinyl butyral resin: 10 weight parts, dioctyl phthalate (DOP) (DOP) as softening agent: 5 weight parts and the ethanol as solvent: 100 weight parts mix and carry out paste in ball mill, obtain dielectric layer paste.
In addition outside above-mentioned, by Ni particle: 44.6 weight parts, Terpineol 350: 52 weight parts, ethyl cellulose: 3 mass parts, benzotriazole: 0.4 weight part is mixing with 3 rollers, carry out paste materialization and make interior electrode layer paste.
Thus use the dielectric layer paste of above-mentioned making, in PET film, the mode becoming 4.5 μm with dried thickness forms raw cook.Next, use interior electrode layer paste thereon, after having printed electrode layer with predetermined pattern, peeling sheet PET film, has made the raw cook with electrode layer.Next, stacked multi-disc has the raw cook of electrode layer, and pressurizing binding makes raw cook duplexer, this raw cook duplexer is cut into the size of regulation, obtains raw cook.
Next, carry out de-adhesive treatment under the following conditions for the raw cook obtained, burn till and anneal, obtain laminated ceramic sintered body.
De-binding agent treatment condition are heat-up rate is 25 DEG C/h, keeps temperature: 235 DEG C, hold-time: 8 hours, atmosphere: in air.
Firing condition is heat-up rate is 200 DEG C/h, and keep temperature to be 1260 DEG C, the hold-time is 2 hours.Cooling rate is 200 DEG C/h.In addition, atmosphere gas is the N of humidification 2+ H 2mixed gas, oxygen partial pressure is 10 -12mPa.
Annealing conditions is heat-up rate is 200 DEG C/h, and the hold-time is 1050 DEG C, and the hold-time is 3 hours, and cooling rate is 200 DEG C/h, and atmosphere gas is the N of humidification 2gas (oxygen partial pressure: 10 -7mPa).
In addition, in the humidification of the atmosphere gas when burning till and anneal, moistener is employed.
Next, carried out by the end face of the laminated ceramic sintered body obtained after cylinder ground, coating Cu cream, as outer electrode, carries out sintering processes under reducing atmosphere, obtains the sample of the laminated ceramic capacitor shown in Fig. 1.The sample of the electric capacity obtained is of a size of 3.2mm × 1.6mm × 0.7mm, and the layer thickness of dielectric layer is 3.0 μm, and internal electrode thickness makes 1.0 μm.In addition, if the number of dielectric layer folded in usual internal electrode increases, the reliability in high temperature load life-span etc. has the tendency of reduction, and therefore, in an embodiment of the present invention, the number of dielectric layer makes the changes that 100 layers are easily observed the high temperature load life-spans.
According to the method shown in following, relative permittivity is measured respectively to the capacitor sample obtained, CR amasss, rate of change of capacitance at 125 DEG C and high temperature load life-span (HALT), sintered compact median size.
(relative permittivity)
Relative permittivity ε rbe 1.0kHz with digital LCR survey meter (YHP company manufacture 4274A) in frequency at reference temperature 25 DEG C, incoming signal level (mensuration voltage) is for measuring capacitor sample under the condition of 1.0Vrms.For capacitor sample, at 150 DEG C, carry out thermal treatment in 1 hour, calculate relative permittivity ε by the electrostatic capacitance value after 24 hours r(there is no unit).Relative permittivity is preferably high, is preferably more than 2200 in the present embodiment.Result is shown in Table 1.
(CR amasss)
Use insulating-resistance meter (AdvantestCorporation manufacture R8340A), be determined at the insulation resistance IR after the volts DS 1 minute applying 25V at 25 DEG C.CR amasss the electrostatic capacitance C(unit μ F by trying to achieve said determination) and insulation resistance IR(unit be M Ω) long-pendingly to calculate.CR is long-pending more high more preferred, and more than 500 is good in the present embodiment, and more than 1000 is good especially.Result is shown in table 1.
(rate of change of capacitance (temperature profile) of 125 DEG C)
Be 1.0kHz in frequency, incoming signal level (mensuration voltage) is under the condition of 1.0Vrms, in-55 DEG C ~ 125 DEG C, electrostatic capacitance is measured to capacitor sample, electrostatic capacitance in 25 DEG C is calculated the velocity of variation Δ C of electrostatic capacitance as standard, evaluate for the temperature profile X7R characteristic whether meeting EIA specification.In the present embodiment, whether have rated rate of change of capacitance Δ C under high temperature side (125 DEG C) is within ± 15%.If the rate of change of capacitance at 125 DEG C meets ± and 15%, the rate of change of capacitance at-55 DEG C also meets X7R characteristic.Result is shown in Table 1.
(high temperature load life-span)
Capacitor sample is kept to the applying state of the volts DS under the electric field of at 175 DEG C 25V/ μm, measure the insulation degradation time of capacitor sample, evaluate the high temperature load life-span.In the present embodiment, by time when reducing by 1 order of magnitude to insulation resistance applying from voltage, the life-span is defined as.In addition, in the present embodiment, carry out above-mentioned evaluation for 20 capacitor samples, the mean-time-between-failure (MTTF) calculated will be analyzed by Weibull be defined as the mean lifetime of this sample.In the present embodiment, using mean lifetime more than 50 hours as good, using more than 100 hours as good especially.Result is shown in Table 1.
(sintered compact median size)
As the measuring method of the average crystallite particle diameter of dielectric particle, first the capacitor sample obtained is cut off along the face perpendicular to internal electrode, grind this cut surface.Then, chemical corrosion is carried out to this abrasive surface, use scanning electronic microscope (SEM) to observe afterwards, count about 1000 particles and the shape of dielectric particle be assumed to spherical and calculate.In embodiment 1, sintered compact median size is 210nm.
As shown in Table 1, when Ra oxide compound, Rb oxide compound, Rc oxide compound, Mg oxide compound and Si oxide compound content within the scope of the invention, meet X7R characteristic, the good high temperature load life-span can be obtained, and can confirm to obtain high relative permittivity.Further, can confirm that at the total amount RT of Ra oxide compound, Rb oxide compound, Rc oxide compound be more than 1.5mol below 2.4mol, and the ratio of components of Ra oxide compound and Mg oxide compound, Si oxide compound is within the scope of the dotted line of Fig. 2, maintain X7R characteristic and the high temperature load life-span especially improves.
At this, Fig. 2 is in sample number 1 ~ 40, for the content sample within the scope of the invention of Ra oxide compound, Rb oxide compound, Rc oxide compound, Mg oxide compound and Si oxide compound, and the figure of the molar ratio of the oxide compound of diagram Ra, Mg, Si.Dotted line and summit zero for diagram is by an A(28,34,38), some B(37,27,37), some C(41,35,24), some D(27,46,27) figure of 4 scopes fenced up.◎ is the sample within the scope of dotted line, and the total amount RT of Ra, Rb, Rc is the sample of more than 1.5mol less than 2.4.
△ be the content of Ra oxide compound, Rb oxide compound, Rc oxide compound, Mg oxide compound and Si oxide compound within the scope of the invention, but the molar ratio of the oxide compound of Ra, Mg, Si 4 institute enclose extraneous sample.
▽ is sample number 23, although be that the molar ratio of the oxide compound of Ra, Mg, Si encloses in scope 4 institutes, the total amount RT of Ra, Rb, Rc is 2.5, the sample at more than 1.5mol and beyond the scope of below 2.4mol.
In fig. 2, the sample that ◎, △, ▽ represent all can obtain preferred characteristic.Wherein, can confirm that the sample represented by ◎ can obtain particularly preferred characteristic in comprehensive evaluation.
In addition, when to load relative to the amount of Ra oxide compound and Si oxide compound as sample number 30 be superfluous Mg oxide compound or as sample 31 relative to Ra oxide compound or Mg oxide compound be Si oxide compound extremely few when, sinter insufficient under this firing condition, the insufficient densification of dielectric layer portion, therefore, the evaluation of each mensuration can not be carried out owing to not conducting.
Sample with ◎ in table 1 is, the content of Ra oxide compound, Rb oxide compound, Rc oxide compound, Mg oxide compound and Si oxide compound within the scope of the invention, the molar ratio of the oxide compound of Ra, Mg, Si in 4 scopes of enclosing, the sample (◎ of Fig. 2) of the total amount RT of further Ra, Rb, Rc at more than 1.5mol and in the scope of below 2.4mol.Sample with ※ is that the content of Ra oxide compound, Rb oxide compound, Rc oxide compound, Mg oxide compound and Si oxide compound is at extraneous sample of the present invention.Do not have marked sample be the content of Ra oxide compound, Rb oxide compound, Rc oxide compound, Mg oxide compound and Si oxide compound within the scope of the invention, but the molar ratio of the oxide compound of Ra, Mg, Si 4 enclose (△ of Fig. 2) outside scope, or the total amount RT of Ra, Rb, Rc is at more than 1.5mol and beyond the scope of below 2.4mol (▽ of Fig. 2).
(embodiment 2)
Except the content of Ra, Rb, Rc is made except described in table 2, make the sample of laminated ceramic capacitor according to the method that embodiment 1 is same, carry out the evaluating characteristics same with embodiment 1.In addition, the composition of the Addition ofelements beyond Ra, Rb, Rc is made with sample number 19 same.Result is shown in Table 2.
[table 2]
Can be confirmed by table 2, when using the element beyond Dy, Ho, Yb as Ra, Rb and Rc, as long as content also can obtain same effect within the scope of the invention.In addition, the sample with ◎ in table 2 is use Dy as Ra, uses Ho, use the sample of Yb as Rc as Rb.In this case, can especially balance obtain well the life-span, relative permittivity, CR amass.
(embodiment 3)
Except make the oxide elements of Ra, Rb, Rc make as described in Table 3 except, other all same with embodiment 1 method make laminated ceramic capacitor, carried out the evaluating characteristics same with embodiment 1.In addition, composition and the sample number 19 of the Addition ofelements beyond Ra, Rb, Rc are same.Result is shown in Table 3.
[table 3]
In table 3, the sample of less than 2 kinds is with the sample of ※ to be rare earth element to be.Confirm in this case, can not get desired characteristic.
(embodiment 4)
Except changing the content of the oxide compound of V and the oxide compound of Mn, and embodiment 1 similarly makes laminated ceramic capacitor, carries out the evaluating characteristics same with embodiment 1.In addition, for sample number 64, Cr is employed 2o 3instead of MnO, sample number 65 and sample number 66 employ WO 3and MoO 3instead of V 2o 5.In addition, the composition of other additive element and sample number 19 same.Result is shown in Table 4.
In table 4, sample V(W, Mo of band ◎) oxide compound and Mn(Cr) the content of oxide compound be the sample of more than 0.05mol below 0.10mol.Can confirm in this case, CR is long-pending and the high temperature load life-span is excellent especially.
(embodiment 5)
Except changing the median size of barium titanate of the raw material forming principal constituent into 130nm(sample number 73), 250nm(sample number 74) except other is all same with embodiment 1, make laminated ceramic capacitor sample, except measuring the median size after sintering, also carry out the evaluating characteristics same with embodiment 1.In addition, the composition of various additive element and sample number 19 same.Result is shown in table 5.
In addition, except the median size of the barium titanate using the raw material as main component makes 200nm, by Ba/Ti ratio according to outside change table 5 Suo Shi, other is all same with embodiment 1, make laminated ceramic capacitor sample (sample number 75a, 75,76,76a), except determining the median size after sintering, also carry out the evaluating characteristics same with embodiment 1.In order to by the Ba/Ti after sintering than the adjustment of the value be set to described in table 5, such as make 1.004 by the u/v of the raw material by barium titanate, in sample number 75, do not add BaO, in sample number 76, outside principal constituent, other interpolation BaO carries out.In addition, the composition of various additive element is identical with sample number 19.Result is shown in Table 5.
[table 5]
As shown in Table 5, although relative permittivity reduces when particle diameter after sintering is little, rate of change of capacitance is deteriorated, and there is excellent tendency in the high temperature load life-span.If the particle diameter after sintering becomes large, although then rate of change of capacitance is excellent, there is the tendency of reduction in the high temperature load life-span.In addition, if Ba/Ti ratio diminishes have rate of change of capacitance variation, the tendency that stability is also deteriorated is burnt till.If Ba/Ti is than large, although then CR sum high temperature load service life reduction, rate of change of capacitance has excellent tendency.

Claims (7)

1. a dielectric ceramic composition, is characterized in that,
Contain as main component with general formula ABO 3the compound of the perovskite type crystal structure represented, wherein, A is at least a kind of being selected from Ba, Ca and Sr, and B is at least a kind of being selected from Ti and Zr,
Following material is contained as minor component relative to compound described in 100mol:
The oxide compound of Ra, is converted into Ra 2o 3for more than 0.6mol and below 1.4mol, wherein Ra is at least a kind of being selected from Dy, Gd and Tb;
The oxide compound of Rb, is converted into Rb 2o 3for more than 0.2mol and below 0.7mol, wherein Rb is at least a kind of being selected from Ho and Y;
The oxide compound of Rc, is converted into Rc 2o 3for more than 0.2mol and below 0.7mol, wherein Rc is at least a kind of being selected from Yb and Lu;
The oxide compound of Mg, is converted into magnesium and is more than 0.6mol and below 1.6mol; And
The oxide compound of Si, is converted into Si and is more than 0.6mol and is less than 1.2mol.
2. dielectric ceramic composition as claimed in claim 1, is characterized in that,
The total amount of the oxide compound of the oxide compound of described Ra, the oxide compound of Rb, Rc is being converted into Ra respectively 2o 3, Rb 2o 3, Rc 2o 3time be more than 1.5mol below 2.4mol, and the molar ratio of the oxide compound of the oxide compound of Ra, Mg, the oxide compound of Si is positioned at the scope of being surrounded by an A (28,34,38), some B (37,27,37), some C (41,35,24), these four points of some D (27,46,27).
3. dielectric ceramic composition as claimed in claim 1 or 2, wherein,
As minor component, further containing the oxide compound being selected from least one in V, Mo and W when being converted into V, Mo and W being 0.05 ~ 0.10mol.
4. dielectric ceramic composition as claimed in claim 1 or 2, wherein,
As minor component, the preferred oxide compound containing when being converted into Mn and Cr being Mn and/or Cr of 0.10 ~ 0.20mol further.
5. dielectric ceramic composition as claimed in claim 1 or 2, wherein,
Median size after sintering is 150nm ~ 260nm.
6. dielectric ceramic composition as claimed in claim 1 or 2, wherein,
Ba/Ti＝1.004～1.015。
7. a ceramic electronic components, wherein,
Have dielectric layer and electrode layer, the dielectric ceramic composition of described dielectric layer according to any one of claim 1 ~ 6 is formed.
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